Thioether-based fragrance precursor compound I

Abstract

The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) derived from mercaptosilanes and selected fragrances, and to a process for their preparation. Furthermore, the present invention relates to detergents or cleaning agents, cosmetic compositions, and a perfume composition containing such fragrance precursor compounds. Furthermore, the present invention relates to a process for the long-lasting perfuming of surfaces using the fragrance precursor compounds and agents according to the invention.

Description

The present invention relates to specific thioether-based fragrance precursor compounds of formula (I) derived from mercaptosilanes and selected fragrances and a process for their preparation. The present invention further relates to detergents and / or cleaners, cosmetic compositions and perfume compositions which comprise such perfume precursor compounds. The present invention further relates to a method for long-lasting fragrancing of surfaces using the fragrance precursor compounds and agents according to the invention.Detergents and / or cleaners or cosmetic compositions usually contain fragrances which impart a pleasant odor to the compositions. The fragrances can also serve to mask the odor of other ingredients, so that a pleasant odor impression is produced at the consumer.In particular in the field of detergents and / or cleaning agents, fragrances are important constituents of the composition, since the laundry should have a pleasant and as fresh as possible fragrance both in the moist and in the dry state. The use of fragrances is fundamentally problematic, since these are compounds which are more or less volatile, but nevertheless a long-lasting fragrance effect is sought. In particular in the case of those fragrances which represent the fresh and light notes of the perfume and are particularly volatile as a result of their high vapor pressure, the desired longevity of the fragrance impression is hardly achievable.Delayed release of odour can be effected, for example, by what are known as fragrance precursor compounds. These perfume precursor compounds are based on perfume compounds, for example perfume aldehydes or ketones, which are reacted with further compounds to form the perfume precursor compounds mentioned, these then being capable of releasing the actual perfume compound again in a delayed manner (for example by hydrolysis or photochemical). It is of particular interest here to release a plurality of different fragrances from a fragrance precursor compound in order to maintain the harmonies of the fragrance impression.WO 2004 / 105713 A1 discloses thioether-based fragrance precursor compounds.The object of the present invention was to provide fragrance precursor compounds which can be obtained by a simple synthesis and which desirably release at least two different fragrances. Furthermore, the perfume precursor compounds should preferably be suitable for use in consumer products, such as, for example, detergents and / or cleaners or cosmetic agents. It is also desirable here that the fragrance precursor compounds also achieve better adhesion to the surface to which they are applied, preferably a textile.The present inventors have found that the object can be achieved by the specific fragrance precursor compounds of formula (I) derived from mercaptosilanes and selected fragrances.In one aspect, the invention therefore relates to a fragrance precursor compound of the formula (I) where R 1 is selected from H, linear or branched C 1- C 5- alkyl groups, linear, branched or cyclic C 6- C 25- alkyl-, C 6- C 25- alkenyl-, C 6- C 25- alkynyl-, C6-C25alkadienyl-, C 6- C 25-- alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups, where at least one R 1 is a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C25alkynyl, C6-C25alkadienyl, C 6- C 25- is an alkatrienyl group or aromatic group, which in turn may be substituted by C 1- C 4- alkyl groups, R 2 and R 3 are independently selected from H, linear, branched or cyclic C 1- C 25- alkyl-, C 1- C 25- alkenyl-, C1-C25alkynyl-, C1-C25alkadienyl-, C 1- C 25- alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups or R 2 and R 3 form with one another a saturated or unsaturated ring having 6 to 20 carbon atoms, including the carbon atoms to which R 2 and R 3 are bonded, this ring in turn being substituted by linear or branched C 1- C 4- alkyl or C1-C4alkenyl groups, R 4 is selected from H and -CH 3 and R 5 is selected from -OR 1 and -CH 3.In a second aspect, the present invention relates to a process for preparing a fragrance precursor compound of formula (I).In a third aspect, the present invention relates to a perfume composition containing at least one perfume precursor compound of the present invention.In a fourth aspect, the present invention relates to a washing and / or cleaning agent comprising at least one fragrance precursor compound of the present invention.In a fifth aspect, the present invention relates to a cosmetic agent containing at least one fragrance precursor compound of the present invention.Finally, in a sixth aspect, the present invention relates to a method for the long-lasting fragrancing of surfaces, characterized in that a perfume precursor compound according to the invention or a perfume composition according to the invention or a washing and / or cleaning agent according to the invention or a cosmetic agent according to the invention is applied to the surface to be fragrancing, wherein fragrancing continues longer than if the respective perfume compound or an identical agent in which the perfume precursor compound is replaced by the respective perfume compound were used.These and other embodiments, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. In this case, individual features or embodiments of the invention described can be combined with other features or embodiments of the invention without these having been described in combination within the scope of the invention. It is understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to the examples."At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of the pro-perfume compounds described herein, this specification does not refer to the absolute amount of molecules, but to the type of compound. "At least one pro-perfume compound" therefore means, for example, that only one type of pro-perfume compound or several different types of pro-perfume compounds may be included without giving any details about the amount of the individual compounds.All amounts given in connection with the process described herein are based, unless otherwise stated, on % by weight, in each case based on the total weight of the composition. Furthermore, such amounts relating to at least one constituent always relate to the total amount of this type of constituent contained in the composition, unless explicitly stated otherwise. That is, such amounts, for example in connection with "at least one pro-perfume compound", refer to the total amount of pre-perfume compounds contained in the composition, unless explicitly stated otherwise.Numerical values indicated herein without decimal places each refer to the full indicated value with one decimal place. For example, "99%" means "99.0%".Numerical ranges indicated in the format "in / from x to y" include the above values. When several preferred numerical ranges are specified in this format, it is understood that all ranges arising from the combination of the various endpoints are also detected."Substituted" as used herein in connection with the definition of the pro-perfume compounds of formula (I) and the compound of formula (II) means that one hydrogen atom is replaced by another radical. Suitable radicals are C 1- C 4- alkyl groups.The terms "perfume" and "perfume" are to be used interchangeably within the scope of this invention. A perfume is a compound which has a characteristic odor and contributes to achieving a specific perfume profile of a perfume oil or composition. Fragrances also include those compounds that alter the fragrance profile of a perfume oil or composition to a degree that the fragrance is to a certain depth, which is commonly known to those skilled in the art as the complexity of a fragrance.The present invention relates in particular to fragrance precursor compounds of the formula (I) where R 1 is selected from H, linear or branched C 1- C 5- alkyl groups, linear, branched or cyclic C 6- C 25- alkyl-, C 6- C 25- alkenyl-, C 6- C 25- alkynyl-, C6-C25alkadienyl-, C 6- C 25-- alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups, where at least one R 1 is a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C25alkynyl, C6-C25alkadienyl, C 6- C 25- is an alkatrienyl group or aromatic group, which in turn may be substituted by C 1- C 4- alkyl groups, R 2 and R 3 are independently selected from H, linear, branched or cyclic C 1- C 25- alkyl-, C 1- C 25- alkenyl-, C1-C25alkynyl-, C1-C25alkadienyl-, C 1- C 25- alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups or R 2 and R 3 form with one another a saturated or unsaturated ring having 6 to 20 carbon atoms, including the carbon atoms to which R 2 and R 3 are bonded, this ring in turn being substituted by linear or branched C 1- C 4- alkyl or C1-C4alkenyl groups, R 4 is selected from H and -CH 3 and R 5 is selected from -OR 1 and -CH 3.Surprisingly, it has been found that fragrance precursor compounds of the formula (I) are capable of releasing two different fragrances, in particular two different types of fragrances. In particular, a fragrance precursor compound of formula (I) may release a fragrance of the α,β-unsaturated ketone or α,β-unsaturated aldehyde type and at least one fragrance alcohol.In a preferred embodiment of the fragrance precursor compound of the formula (I), R is 2 or R is 3 of the type and the respective other radical R is 2 or R is 3 -CH 3 and R is 4 H.Perfume precursor compounds of formula (I) having these substituents for R 2, R 3 and R 4 release ionone, damascenone and / or damascone. Ionones, damascenones and damascone are a number of closely related chemical compounds which are part of a variety of essential oils. They belong to a family of chemicals called rose ketones. Rose ketones as perfumes are of great economic interest.In a further preferred embodiment, in the fragrance precursor compound of formula (I), R 2 and R 3 form a ring of type and R 4 is -CH 3.Pro-perfume compounds of formula (I) having these substituents for R 2, R 3 and R 4 release carvone. Both enantiomers of carvone are part of different essential oils.It is further preferred that R 1 is derived from a perfume alcohol of formula R 1- OH.R 1 of the perfume alcohol is a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C 25- alkynyl, C 6- C 25- alkadienyl, C 6- C25alkatrienyl group or aromatic group, which in turn may be substituted with C1-C4alkyl groups.The perfume alcohol of the formula R 1- OH is very particularly preferably selected from the group consisting of 2-phenylethanol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butylcyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, alpha-methylbenzyl alcohol, alpha-terpineol, benzyl alcohol, beta-terpineol, citronellol, Decanol, dihydromyrcenol, dimethylbenzyl carbinol, dimethylheptanol, dimethyloctanol, ethylvaniline, eugenol, geraniol, heptanol, isobornyl, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, para-menthane-7-ol, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-nonen-1-ol, trans-2-octenol, undecanol, vanillin, cinnam alcohol, cis-hex-3-en-1-ol and mixtures thereof.2-Phenylethanol smells of roses and is advantageously used together with at least one of the rose ketones in the fragrance precursor compounds of formula (I).Likewise, the perfume alcohol of the formula R 1- OH is particularly advantageously selected from the group consisting of citronellol, geraniol, cis-hex-3-en-1-ol and mixtures thereof.In a preferred embodiment, at least two R 1 are a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C 25- alkynyl, C 6- C 25- alkadienyl, C 6- C25alkatrienyl group or aromatic group, which in turn may be substituted with C1-C4alkyl groups. The at least two R 1 may be the same or different, wherein the at least two R 1 are preferably the same.In this embodiment of the invention, two perfume alcohols of the formula R 1- OH are liberated per perfume precursor compound of the formula (I).In a likewise preferred embodiment, R is 5- OR 1 and all R 1 are a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C 25- alkynyl, C 6- C25-alkadienyl, C6-C25-alkatrienyl group or aromatic group, which in turn may be substituted with C1-C4-alkyl groups. The three R 1 may be the same or different, the three R 1 preferably being the same.In this embodiment of the invention, two perfume alcohols of the formula R 1- OH are liberated per perfume precursor compound of the formula (I).From the described perfume precursor compounds of formula (I), the perfume or perfumes can be released by hydrolysis, especially at acidic pH values, i.e. pH values < 7, for example < 6 or < 5.The perfume precursor compounds of formula (I) are obtained by a two-step reaction. In a first step, a compound of the formula (II) is reacted with a mercaptosilane.For the compound of formula (II), R 2 and R 3 are independently selected from H, linear, branched or cyclic C 1- C 25- alkyl, C 1- C 25- alkenyl, C 1- C 25- alkynyl, C 1- C 25- alkadienyl, C1-C25alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups, or R 2 and R 3 including the carbon atoms to which R 2 and R 3 are bonded, together form a saturated or unsaturated ring having 6 to 20 carbon atoms, where this ring may in turn be substituted by linear or branched C 1- C 4- alkyl or C 1- C 4- alkenyl groups and R4is selected from H and -CH3.In various particularly preferred embodiments of the invention, the compound of the formula (II) can be selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone and mixtures thereof.It is further preferred that the mercaptosilane is selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxysilane, 3-mercaptopropyldiethoxymethylsilane, and mixtures thereof. The mercaptosilane is preferably selected from 3-mercaptopropyltriethoxysilane and 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyltriethoxysilane being preferred.The reaction of the compound of the formula (II) and the mercaptosilane takes place preferably in air or under a nitrogen atmosphere. The reaction can be carried out in bulk or in a suitable solvent. A suitable solvent is, for example, dichloromethane, tetrahydrofuran or acetone. Preferably, a non-nucleophilic base, for example 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), is also used. The reaction mixture of the starting materials, optionally the base and the solvent is then preferably stirred at room temperature for a plurality of hours, preferably 2 to 60, in particular 12 to 48. The reaction product obtained is isolated and optionally purified by conventional methods, for example, liquid-liquid extraction or column chromatography.In a second step, the reaction product obtained in step 1 is reacted with a perfume alcohol of the formula R 1- OH, where R 1 of the perfume alcohol is a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C 25- alkynyl, C 6- C 25- alkadienyl, C6-C25-alkatrienyl group or aromatic group, which may in turn be substituted by C 1- C 4- alkyl groups.In a preferred embodiment, the perfume alcohol of the formula R 1- OH is selected from the group consisting of 2-phenylethyl alcohol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butylcyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, alpha-methylbenzyl alcohol, alpha-terpineol, benzyl alcohol, beta-terpineol, Citronellol, decanol, dihydromyrcenol, dimethylbenzyl carbinol, dimethylheptanol, dimethyloctanol, ethylvaniline, eugenol, geraniol, heptanol, isobornyl, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, para-menthane-7-ol, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-nonen-1-ol, trans-2-octenol, undecanol, vanillin, cinnam alcohol, cis-hex-3-en-1-ol, and mixtures thereof.In a preferred embodiment of the process, a compound of the formula (II) selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone and mixtures thereof and a perfume alcohol of the formula R 1- OH selected from the group consisting of 2-phenylethyl alcohol, citronellol, geraniol, cis-hex-3-en-1-ol and mixtures thereof are used in the process.In a preferred embodiment of the process, a compound of the formula (II) selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone and mixtures thereof and 2-phenylethyl alcohol are used as perfume alcohol of the formula R 1- OH.In a further preferred embodiment of the process, a compound of the formula (II) selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone and mixtures thereof and citronellol are used as perfume alcohol of the formula R 1- OH.In yet another preferred embodiment of the process, a compound of the formula (II) selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone and mixtures thereof and geraniol are used as perfume alcohol of the formula R 1- OH.In a likewise preferred embodiment of the process, a compound of the formula (II) selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone and mixtures thereof and cis-hex-3-en-1-ol are used as perfume alcohol of the formula R 1- OH.Surprisingly, it has been found that the usually short-chain alkoxy groups of the mercaptosilanes, in particular the methoxy or ethoxy groups, can be replaced without problems by alkoxy groups which are derived from fragrance alcohols of the formula R 1- OH.This results in fragrance precursor compounds of formula (I) capable of releasing at least two different fragrances, in particular two different types of fragrances.The reaction product obtained in step 1 is usually reacted with the perfume alcohol R 1- OH in air. Further, the reaction is preferably carried out without a solvent. The perfume alcohol R 1- OH is preferably used in excess and simultaneously serves as solvent or reaction medium. Preferably, a strong base, for example potassium hydroxide, is also used. The reaction mixture of the reaction product obtained in step 1, the perfume alcohol R 1- OH and the base is then preferably stirred for several hours, preferably 2 to 60, in particular 10 to 48, at elevated temperature and / or under reduced pressure. The reaction product obtained is isolated by conventional methods and, if appropriate, purified.The present invention further relates to perfume compositions, detergents and / or cleaners or cosmetic compositions containing at least one of the perfume precursor compounds of the present invention.In a preferred embodiment, the at least one fragrance precursor compound is contained in a total amount of 0.01 to 20 wt %, advantageously of 0.1 to 15 wt %, particularly preferably of 0.5 to 10 wt %, in each case based on the total weight of the perfume composition.In preferred embodiments, the at least one fragrance precursor compound is present in a total amount of from 0.001 to 5 wt %, advantageously from 0.005 to 3 wt %, particularly preferably from 0.01 to 1 wt %, in each case based on the total weight of the washing and / or cleaning agent or cosmetic agent.The above-described perfume precursor compounds of formula (I) can be used in a perfume composition, a washing and / or cleaning agent or a cosmetic agent as mixtures with at least one further perfume or at least one further perfume precursor compound which is different from the perfume precursor compound of formula (I).The further fragrances, which may optionally be present in the perfume composition, the washing or cleaning agent or the cosmetic agent, are not subject to any particular restrictions. Thus, individual perfume compounds of natural or synthetic origin, for example of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon types, can be used. Perfume compounds of the ester type include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate and jasmacyclate. The ethers include, for example, benzyl ethyl ether and ambroxan; the aldehydes include the abovementioned, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde (3-(4-propan-2-ylphenyl)butanal), lilial and bourgeonal; the ketones include, for example, the ionones, [alpha]-isomethylionone and methyl cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used which together produce an appealing scent note.The compositions may also contain natural perfume mixtures as are available from vegetable sources, e.g., pine, citrus, jasmine, patcholoy, rose, or ylang-ylang oil. Also suitable are muscatell sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and also orange blossom oil, neroli oil, orange peel oil and sandalwood oil. Further conventional fragrances which may be present in the compositions according to the invention in the context of the present invention are, for example, the essential oils such as angelica root oil, anis oil, arnica flower oil, basil oil, bay oil, Champacablütenöl edeltannic oil, edeltann cone oil, elemi oil, eucalyptus oil, fenchel oil, spruce needle oil, galbanum oil, geranium oil, gingegras oil, guajacwood oil, gurujunbalam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, kalmus oil, chamomillen oil, and the like, Camphor oil, canaga oil, cardiomene oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, herbal mint oil, cowmel oil, kumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, mossy grain oil, myrrhen oil, clove oil, neroli oil, niaouli oil, olibanum oil, origanum oil, palmarosa oil, patchuli oil, perubalsam oil, petitgraine oil, pepper oil, peppermint oil, pement oil, pine oil, rose oil, Rosemary oil, sandalwood oil, celery oil, spik oil, sternal anis oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiger oil, juniper beer oil, wermut oil, wneter green oil, Ylang-Ylang oil, Ysop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil, and zygpress oil, as well as ambrettolide, ambroxan, α-amylcinnamaldehyde, anethol, anisaldehyde, anis alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, Benzyl formate, benzyl valerate, borneol, bornyl acetate, boisambrene forte, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptus, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iran, isoeugenol, isoeugenol methyl ether, isosefrol, jasmone, camphor, carvacrool, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, Methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavikol, p-methyl quinoline, methyl β-naphthyl ketone, methyl n-nonyl acetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy acetophenone, pentadecanoylide, β-phenylethyl alcohol, phenylacetic acid, pulegone, safrol, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, santalol, sandelice, skatol, terpineol, thymene, thymol, troenan, γ-undelactone, vanillin, veratralaldehyde, cinnamic aldehyde, cinnamic alcohol, cinnamic acid, ethyl cinnamic acid ester, benzyl cinnamic acid ester, diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal and mixtures thereof.It is possible in particular for the at least one fragrance precursor compound of the formula (I) to be used with the corresponding α,β-unsaturated aldehydes and / or α,β-unsaturated ketones. According to a preferred embodiment, such compositions are distinguished in that the molar ratio of perfume aldehyde and / or perfume ketone to the corresponding precursor compound of formula (I) is 20:1 to 1:20, preferably 10:1 to 1:10, more preferably 5:1 to 1:5, even more preferably 3:1 to 1:3, even more preferably 2:1 to 1:2 and in particular 1.2:1 to 1:1.2. Likewise, the at least one fragrance precursor compound of the formula (I) can alternatively or additionally be present together with the fragrance alcohol R 1- OH.A perfume composition can comprise, in addition to the at least one fragrance precursor compound of the formula (I) and the optional, further fragrances or natural fragrance mixtures, further ingredients, in particular a carrier material, such as dipropylene glycol, diethyl phthalate, isopropyl myristate or ethyl citrate.In addition to the at least one fragrance precursor compound of the formula (I), detergents and cleaners may also comprise, in particular, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants or mixtures thereof. Furthermore, these agents can be present in solid or liquid form.Suitable nonionic surfactants are, in particular, ethoxylation and / or propoxylation products of alkyl glycosides and / or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, which correspond with respect to the alkyl moiety to the long-chain alcohol derivatives mentioned, and of alkyl phenols having 5 to 12 C atoms in the alkyl radical, are usable.Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Soaps which can be used are preferably the alkali metal salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful sulfate surfactants include the salts of the sulfuric monoesters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of the above-mentioned nonionic surfactants having a low degree of ethoxylation. Surfactants of the sulfonate type which can be used include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl part, alkanesulfonates having 12 to 18 carbon atoms, and olefinsulfonates having 12 to 18 carbon atoms which are formed during the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfo fatty acid esters which are formed during the sulfonation of fatty acid methyl esters or ethyl esters. Cationic surfactants are preferably selected from esterquats and / or quaternary ammonium compounds (QAV) according to the general formula (R I)( R II)( R III)( R III) N + X - in which R I to R IV are identical or different C 1-22- alkyl radicals, C 7-28- arylalkyl radicals or heterocyclic radicals, two or, in the case of an aromatic bond as in pyridine, even three radicals together with the nitrogen atom forming the heterocycle, e.g. a pyridinium or imidazolinium compound, and X - represents halide ions, sulfate ions, hydroxide ions or similar anions. QAVs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines having a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines having two long radicals and one methyl group can also be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are sparingly reactive and are quaternized, for example, with dimethyl sulfate. QAVs which can be used are, for example, benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalcon B (m,p-dichlorobenzyldimethyl-C 12- alkylammonium chloride, benzoxonium chloride (benzyldodecylbis(2-hydroxyethyl)ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethylammonium bromide), benzetonium chloride (N,N dimethyl-N [2-[2-[p-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, 1-cetylpyridinium chloride and thiazoline iodide, and mixtures thereof. Preferred QAVs are the benzalkonium chlorides with C 8- C 22- alkyl radicals, in particular C 12- C 14- alkylbenzyldimethylammonium chloride.Preferred ester quats are methyl-N-(2-hydroxyethyl)-N,N-di(tallowacyloxyethyl)ammonium methosulfate, bis-(palmitoyl)ethyl hydroxyethylmethylammonium methosulfate or methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate. Commercially available examples are the Methylhydroxyalkyldialkoyloxyalkylammoniummethosulfate marketed by Stepan under the trade name Stepantex ® or the products from BASF SE known under the trade name Dehyquart ® or the products from Evonik, known under the name Rewoquat ® respectively.The detergents and cleaners may also contain further ingredients which further improve the application and / or aesthetic properties of the composition, depending on the intended use. In the context of the present invention, they may comprise builders, bleaches, bleach activators, bleach catalysts, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescent agents, dyes, hydrotropes, foam inhibitors, antiredeposition agents, solvents, enzymes, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, color stabilizers, wetting improvers, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, rinse aids, preservatives, antistatic agents, ironing auxiliaries, repellents and impregnating agents, pearlescent agents, polymers, anti-swell agents and anti-slip agents and UV absorbers, without being restricted thereto.In addition to just the at least one fragrance precursor compound of the formula (I), cosmetic agents can comprise further typical ingredients for cosmetic agents. Further suitable ingredients include, in particular, anionic surfactants, amphoteric / zwitterionic surfactants, nonionic surfactants, cationic surfactants, nonionic polymers, anionic polymers, cationic polymers, amphoteric polymers, fatty substances, waxes, protein hydrolysates, amino acids, oligopeptides, vitamins, provitamins, vitamin precursors, betaines, bioquinones, purine (derivatives), taurine (derivatives), plant extracts, silicones, ester oils, UV light protection filters, structuring agents, thickeners, electrolytes, pH adjusters, swelling agents, dyes, anti-scaling active ingredients, complexing agents, opacifiers, pearlescent agents, pigments, stabilizers, propellants, antioxidants, perfume oils and / or preservatives.The amounts of the individual ingredients in the detergents and / or cleaners and in the cosmetic agents are each oriented to the intended use of the agent in question, and the skilled worker is familiar in principle with the orders of magnitude of the amounts of the ingredients to be used or can derive these from the associated technical literature.What has been said about the perfume precursor compound of the formula (I), the perfume composition, the washing and / or cleaning agent and the cosmetic agent applies mutatismutatally to its use in a process for long-lasting fragrancing of surfaces. In the method, at least one fragrance precursor compound of the formula (I) according to the invention, a perfume composition according to the invention, a washing and / or cleaning agent according to the invention or a cosmetic agent according to the invention are applied to the surface to be perfumed. The fragrancing thereby continues longer than if the respective perfume compound or an identical agent in which the perfume precursor compound is replaced by the respective perfume compound(s) were used.ExamplesExample 1: Synthesis of a Perfume Precursor Compound of Formula (I)Step 1: Reaction of α-damascone with 3-mercaptopropyltriethoxysilane3,69 g (15 mmol) of 3-mercaptopropyltriethoxysilane were placed in a flask and dissolved in 100 ml of acetone. Then, 2.88 g (15 mmol) of α-damascone were first added and, after stirring for 5 min, 0.12 g of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) was added. The reaction solution was stirred at room temperature for 46 hours and then completely concentrated in vacuo. The crude product was dissolved in 100 ml of acetone and 8 spatulas of silica gel were added. The acetone was then removed in vacuo and the residue purified using CombiBlue Rf (80 g silica column, hexane / EtOAc 3:1). 4.4 g of a pale yellow liquid product of 95% purity (NMR) were obtained.Step 2: Reaction of the reaction product from Step 1 with 2-phenylethyl alcohol4,95 g (10.9 mmol) of the reaction product from step 1 (3-((3-(triethoxysilyl)propyl)thio)-1-damascone) was placed in a flask together with 4.04 g (32.7 mmol) of 2-phenylethyl alcohol and stirred. 10 mg of finely ground KOH were then added with stirring and the reaction solution was heated to 110° C. After 1 h, the mixture was stirred under reduced pressure (about 150 mbar) for a further 5 h. The mixture was then heated further at 110° C. and stirred under reduced pressure (about 100 mbar) for a further 7 h. The mixture was then heated to 130° C. and stirred under reduced pressure (about 100 mbar) for a further 5 h. The mixture was then cooled to room temperature. 6.07 g of yellowish, clear, slightly viscous product having a purity of 97% (NMR) are obtained.Example 2: Odor TestsThe perfume release was investigated in a fabric softener, in a liquid detergent and in a powder detergent.To this end, perfume-free formulations of the fabric softener, of the liquid detergent and of the powder detergent were in each case admixed with the fragrance precursor compound prepared in Example 1 or with a mixture of equimolar amounts of the two fragrances α-damascone and 2-phenylethyl alcohol as follows and used in a washing / rinsing test in a washing machine.Fabric softener0.31 wt % α-damascone + 0.59 wt % 2-phenylethyl alcohol ii 1.09 wt % fragrance precursor compound of the invention from Example 1Liquid Detergent0.24% by weight of α-damascone + 0.46% by weight of 2-phenylethyl alcohol ii 0.85% by weight of fragrance precursor compound according to the invention from Example 1Powder Laundry Detergent0.14 wt.% α-damascone+0.26 wt.% 2-phenylethyl alcohol ii 0.49 wt.% fragrance precursor compound according to the invention from Example 1Laundry treated with one of the six agents (cotton, polyester, semi-lines) was removed from the washing machine, dried and after 7 days, assessed olfactory for odor intensity by a trained panel on an intensity scale of 1-6 (1: no odor perceptible; 6: very strong odor perceptible).The following table shows the results of odor intensity on various tissues:Fabric softener / cotton23,2Fabric softener / polyester1,52,5Fabric softeners / semi-lines23,2Liquid Laundry Detergent / Cotton1,33,5Liquid Detergent / Polyester1,32,5Liquid Detergent / Semilinen1,23,2Powder Laundry Detergent / Cotton1,83,3Powder Laundry Detergent / Polyester1,83,3Powder Detergent / Semilinen1,82,8In formulations ii, i.e. when the fragrance precursor compound from example 1 is used instead of a mixture of the two fragrances, a higher odor intensity is consistently exhibited.Example 3: Example 3:Step 1: Reaction with L-Carvone with 3-mercaptopropyltriethoxysilane3,0 g (20 mmol) of L-carvone and 4.92 g (20 mmol) of 3-mercaptopropyltriethoxysilane were placed in a flask under a nitrogen atmosphere. 0.03 g (0.2 mmol) of DBU was added. The reaction solution was stirred for 42 hours at room temperature. Subsequently, the reaction solution was poured into 50 ml of cold HCl (5%) with stirring. The HCl phase was then extracted with 100 ml of diethyl ether. The organic phase was washed three times with 100 ml of water, once with 100 ml of saturated NaHCO 3- solution and once with 70 ml of saturated NaCl solution. The organic phase was then dried over MgSO 4 filtered and concentrated completely in vacuo. 6.76 g of product 3-((3-(triethoxysilyl)propyl)thio) carvone (95% purity) resulted.Step 2: Reaction of the reaction product from Step 1 with cis-hex-3-en-1-ol4,1 g (10 mmol) of 3-((3-(triethoxysilyl)propyl)thio)-carvone (95% purity) were initially charged with 4.1 g (40 mmol) of cis-hex-3-en-1-ol in a flask equipped with a distillation bridge and stirred. 9 mg of finely ground KOH were then added with stirring and the reaction solution was heated to 110° C. (heating block). A reduced pressure (about 150 mbar) was applied at intervals of 90 min until the distillate condensed in the distillation bridge. After a reaction time of 7 h, the mixture was cooled to room temperature. The reaction solution was freed from excess cis-hex-3-en-1-ol on a rotary evaporator (75° C., 5 mbar) and in a bulb tube distillation (50° C., 0.04 mbar). 4.61 g of product having a purity of 85% were obtained.Example 4: Example 4:Step 1: Reaction of α-damascone with 3-mercaptopropyltriethoxysilane3,85 g (20 mmol) of α-damascone and 4.92 g (20 mmol) of 3-mercaptopropyltriethoxysilane were placed in a flask under a nitrogen atmosphere. 0.03 g (0.2 mmol) of DBU was added to this reaction mixture. The reaction solution was stirred at room temperature for 24 hours and then poured into 50 ml of cold HCl (5%) with stirring. The HCl phase was then extracted with 100 ml of diethyl ether. The organic phase was washed three times with 100 ml of water, once with 100 ml of saturated NaHCO 3- solution and once with 70 ml of saturated NaCl solution. The organic phase was then dried over MgSO 4 filtered and concentrated completely in vacuo. 7.78 g of product 3-((3-(triethoxysilyl)propyl)thio)-1-damascone (90% purity) were obtained.Step 2, the reaction of 3-((3-(triethoxysilyl)propyl)thio)-1-damascone with phenylethyl alcohol, was carried out as described in Step 2 of Example 1.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Patent Literature citedWO 2004 / 105713 A1

[0005]

Claims

A perfume precursor compound of formula (I) wherein R 1 is selected from H, linear or branched C 1- C 5- alkyl groups, linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C 25- alkynyl, C6-C25alkadienyl, C6-C25-alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups, where at least one R 1 is a linear, branched or cyclic C 6- C 25- alkyl group, C 6- C 25- alkenyl group, C 6- C 25- alkynyl group, C 6- C25alkadienyl group, C6C25alkatrienyl group or aromatic group, which may in turn be substituted by C 1- C 4- alkyl groups, R 2 and R 3 are selected independently of one another from H, linear, branched or cyclic C 1- C 25- alkyl, C 1- C 25- alkenyl, C 1- C 25- alkynyl, C1-C25alkadienyl, C1-C25alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups or R 2 and R 3 may together form a saturated or unsaturated ring having 6 to 20 carbon atoms, including the carbon atoms to which R 2 and R 3 are bonded, which ring may in turn be substituted by linear or branched C 1- C 4- alkyl or C 1- C 4- alkenyl groups, R 4 is selected from H and -CH 3 and R 5 is selected from -OR 1 and -CH 3.A perfume precursor compound according to claim 1, characterized in that R 2 or R 3 is of the type, the other radical R is 2 or R is 3- CH 3 and R is 4 H.A perfume precursor compound according to claim 1, characterized in that R 2 and R 3 form a ring of type and R 4- is CH 3.Fragrance precursor compound according to one of Claims 1 to 3, characterized in that at least one R 1 is derived from a fragrance alcohol of the formula R 1- OH.Fragrance precursor compound according to Claim 4, characterized in that the fragrance alcohol of the formula R 1- OH is selected from the group consisting of 2-phenylethanol, 2-phenylethyl alcohol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butycyclohexanol, 6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, alpha-methylbenzyl alcohol, alpha-terpineol, benzyl alcohol, beta-terpineol, citronellol, decanol, dihydromyrcenol, dimethylbenzyl carbinol, dimethylheptanol, dimethyloctanol, ethylvaniline, eugenol, geraniol, heptanol, isobornyl, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, para-menthane-7-ol, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-nonen-1-ol, trans-2-octenol, undecanol, vanillin, cinnamic alcohol, cis-hex-3-en-1-ol and mixtures thereof.A process for the preparation of a perfume precursor compound of formula (I) wherein R 1 is selected from H, linear or branched C 1- C 5- alkyl groups, linear, branched or cyclic C 6- C 25- alkyl-, C 6- C 25- alkenyl-, C 6- C 25- alkynyl-, C6-C25alkadienyl-, C 6- C 25-- alkatrienyl groups or aromatic groups, which may each be substituted by linear or branched C 1- C 4- alkyl groups, where at least one R 1 is a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C25alkynyl, C6-C25alkadienyl, C 6- C 25-- is an alkatrienyl group or aromatic group, which in turn may be substituted by C 1- C 4- alkyl groups, R 2 and R 3 are independently selected from H, linear, branched or cyclic C 1- C 25- alkyl-, C 1- C 25- alkenyl-, C1-C25alkynyl-, C1-C25alkadienyl-, C 1- C 25- alkatrienyl groups or aromatic groups, each of which may be substituted with linear or branched C 1- C 4- alkyl groups, or R 2 and R 3 form with each other a saturated or unsaturated ring having 6 to 20 carbon atoms, including the carbon atoms to which R 2 and R 3 are bonded, wherein this ring may in turn be substituted by linear or branched C 1- C 4- alkyl or C 1- C 4- alkenyl groups and R 4 is selected from H and -CH 3 and R 5 is selected from -OR 1 and -CH 3 characterized in that in a first step a compound of the formula (II) is reacted with a mercaptosilane and in a second step the reaction product from the first step is reacted with a perfume alcohol of the formula R1-OH, where R 1 of the perfume alcohol is a linear, branched or cyclic C 6- C 25- alkyl, C 6- C 25- alkenyl, C 6- C 25- alkynyl, C 6- C 25- alkadienyl, C 6- C25-alkatrienyl group or aromatic group, which in turn may be substituted with C25-C25-alkyl groups.The method according to claim 6, characterized in that the mercaptosilane is selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane and mixtures thereof.Process according to claim 6 or 7, characterized in that the compound of formula (II) is selected from the group consisting of α-ionone, β-ionone, γ-ionone, α-damascenone, β-damascenone, γ-damascenone, δ-damascenone, α-damascone, β-damascone, γ-damascone, δ-damascone, L-carvone, D-carvone and mixtures thereof.Process according to any of Claims 6 to 8, characterized in that the perfume alcohol of the formula R 1- OH is selected from the group consisting of 2-phenylethyl alcohol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butylcyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol, 6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, alpha-methylbenzyl alcohol, alpha-terpineol, benzyl alcohol, beta-terpineol, citronellol, decanol, dihydromyrcenol, dimethylbenzyl carbinol, dimethylheptanol, dimethyloctanol, ethylvaniline, eugenol, geraniol, heptanol, isobornyl, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, para-menthane-7-ol, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-nonen-1-ol, trans-2-octenol, undecanol, vanillin, cinnamic alcohol, cis-hex-3-en-1-ol and mixtures thereof.Perfume composition containing at least one perfume precursor compound (I) according to any one of claims 1 to 5, wherein the compound is preferably contained in a total amount of from 0.01 to 20 wt.%, advantageously from 0.1 to 15 wt.%, more advantageously from 0.5 to 10 wt.%, based on the total weight of the perfume composition.Cosmetic agent containing at least one fragrance precursor compound (I) according to one of Claims 1 to 5, wherein the compound is preferably contained in a total amount of 0.001 to 5 wt.%, advantageously of 0.005 to 3 wt.%, further advantageously of 0.01 to 1 wt.%, based on the total weight of the agent.Washing and / or cleaning agent, comprising at least one fragrance precursor compound (I) according to any of Claims 1 to 5, wherein the compound is preferably contained in a total amount of from 0.001 to 5% by weight, advantageously from 0.005 to 3% by weight, further advantageously from 0.01 to 1% by weight, based on the total weight of the agent.A method for long-lasting fragrancing surfaces, characterized in that a fragrance precursor compound (I) according to any one of claims 1 to 5 or an agent according to claim 10, 11 or 12 is applied to the surface to be fragrancing, wherein the fragrancing lasts longer than if the respective fragrance compound(s) or an identical agent in which the fragrance precursor compound(s) is / are replaced by the respective fragrance compound(s) were used.